Method for preparing a supported catalyst system and its use in a polymerization process

ABSTRACT

The present invention relates to a composition of carboxylate metal salt and a flow improver useful in combination with a polymerization catalyst to improve the flowability and bulk density of the catalyst. The invention also relates to a polymerization process using the catalyst.

RELATED APPLICATION DATA

[0001] The present application is a divisional of U.S. patentapplication Ser. No. 09/731,635, filed Dec. 7, 2000, now issued as U.S.Pat. No. ______, which claims priority from Provisional U.S. applicationSer. No. 60/170,984 filed Dec. 15, 1999, and is herein incorporated byreference.

FIELD OF THE INVENTION

[0002] The present invention relates to a method for preparing asupported catalyst system and for its use in a process for polymerizingolefin(s). In particular, the invention is directed to a carboxylatemetal salt that has an improved flowability. Specifically, the inventionrelates to a method for preparing a supported bulky ligandmetallocene-type catalyst system including a carboxylate metal salt thathas an improved flowability.

BACKGROUND OF THE INVENTION

[0003] Advances in polymerization and catalysis have resulted in thecapability to produce many new polymers having improved physical andchemical properties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization-type (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes. Especially illustrativeof these advances is the development of technology utilizing bulkyligand metallocene-type catalyst systems. In particular, in a slurry orgas phase process where typically a supported catalyst system is used,there are a variety of different methods described in the art forsupporting bulky ligand metallocene-type catalyst systems. Regardless ofthese technological advances in the polyolefin industry, commonproblems, as well as new challenges associated with process operabilitystill exist. For example, the tendency for a gas phase or slurry phaseprocess to foul and/or sheet remains a challenge.

[0004] Evidence of, and solutions to, various process operabilityproblems have been addressed by many in the art. For example, U.S. Pat.Nos. 4,792,592, 4,803,251, 4,855,370 and 5,391,657 all discusstechniques for reducing static generation in a polymerization process byintroducing to the process for example, water, alcohols, ketones, and/orinorganic chemical additives; PCT publication WO 97/14721 published Apr.24, 1997 discusses the suppression of fines that can cause sheeting byadding an inert hydrocarbon to the reactor; U.S. Pat. No. 5,627,243discusses a new type of distributor plate for use in fluidized bed gasphase reactors; PCT publication WO 96/08520 discusses avoiding theintroduction of a scavenger into the reactor; U.S. Pat. No. 5,461,123discusses using sound waves to reduce sheeting; U.S. Pat. No. 5,066,736and EP-A1 0 549 252 discuss the introduction of an activity retarder tothe reactor to reduce agglomerates; U.S. Pat. No. 5,610,244 relates tofeeding make-up monomer directly into the reactor above the bed to avoidfouling and improve polymer quality; U.S. Pat. No. 5,126,414 discussesincluding an oligomer removal system for reducing distributor platefouling and providing for polymers free of gels; EP-A1 0 453 116published Oct. 23, 1991 discusses the introduction of antistatic agentsto the reactor for reducing the amount of sheets and agglomerates; U.S.Pat. No. 4,012,574 discusses adding a surface-active compound, aperfluorocarbon group, to the reactor to reduce fouling; U.S. Pat. No.5,026,795 discusses the addition of an antistatic agent with a liquidcarrier to the polymerization zone in the reactor; U.S. Pat. No.5,410,002 discusses using a conventional Ziegler-Nattatitanium/magnesium supported catalyst system where a selection ofantistatic agents are added directly to the reactor to reduce fouling;U.S. Pat. Nos. 5,034,480 and 5,034,481 discuss a reaction product of aconventional Ziegler-Natta titanium catalyst with an antistat to produceultrahigh molecular weight ethylene polymers; U.S. Pat. No. 3,082,198discusses introducing an amount of a carboxylic acid dependent on thequantity of water in a process for polymerizing ethylene using atitanium/aluminum organometallic catalysts in a hydrocarbon liquidmedium; and U.S. Pat. No. 3,919,185 describes a slurry process using anonpolar hydrocarbon diluent using a conventional Ziegler-Natta-type orPhillips-type catalyst and a polyvalent metal salt of an organic acidhaving a molecular weight of at least 300.

[0005] There are various other known methods for improving operabilityincluding coating the polymerization equipment, for example, treatingthe walls of a reactor using chromium compounds as described in U.S.Pat. Nos. 4,532,311 and 4,876,320; injecting various agents into theprocess, for example PCT Publication WO 97/46599 published Dec. 11, 1997discusses feeding into a lean zone in a polymerization reactor anunsupported, soluble metallocene-type catalyst system and injectingantifoulants or antistatic agents into the reactor; controlling thepolymerization rate, particularly on start-up; and reconfiguring thereactor design.

[0006] Others in the art to improve process operability have discussedmodifying the catalyst system by preparing the catalyst system indifferent ways. For example, methods in the art include combining thecatalyst system components in a particular order; manipulating the ratioof the various catalyst system components; varying the contact timeand/or temperature when combining the components of a catalyst system;or simply adding various compounds to the catalyst system. Thesetechniques or combinations thereof are discussed in the literature.Especially illustrative in the art is the preparation procedures andmethods for producing bulky ligand metallocene-type catalyst systems,more particularly supported bulky ligand metallocene-type catalystsystems with reduced tendencies for fouling and better operability.Examples of these include: WO 96/11961 published Apr. 26, 1996 discussesas a component of a supported catalyst system an antistatic agent forreducing fouling and sheeting in a gas, slurry or liquid poolpolymerization process; U.S. Pat. No. 5,283,278 is directed towards theprepolymerization of a metallocene catalyst or a conventionalZiegler-Natta catalyst in the presence of an antistatic agent; U.S. Pat.No. 5,332,706 and 5,473,028 have resorted to a particular technique forforming a catalyst by incipient impregnation; U.S. Pat. Nos. 5,427,991and 5,643,847 describe the chemical bonding of non-coordinating anionicactivators to supports; U.S. Pat. No. 5,492,975 discusses polymer boundmetallocene-type catalyst systems; U.S. Pat. No. 5,661,095 discussessupporting a metallocene-type catalyst on a copolymer of an olefin andan unsaturated silane; PCT publication WO 97/06186 published Feb. 20,1997 teaches removing inorganic and organic impurities after formationof the metallocene-type catalyst itself; PCT publication WO 97/15602published May 1, 1997 discusses readily supportable metal complexes; PCTpublication WO 97/27224 published Jul. 31, 1997 relates to forming asupported transition metal compound in the presence of an unsaturatedorganic compound having at least one terminal double bond; and EP-A2-811638 discusses using a metallocene catalyst and an activating cocatalystin a polymerization process in the presence of a nitrogen containingantistatic agent.

[0007] While all these possible solutions might reduce the level offouling or sheeting somewhat, some are expensive to employ and/or maynot reduce fouling and sheeting to a level sufficient to successfullyoperate a continuous process, particularly a commercial or large-scaleprocess.

[0008] Applicants discovered that using a carboxylate metal salt inconjunction with a bulky ligand metallocene-type catalyst system,preferably a supported bulky ligand metallocene-type catalyst system,substantially improves process operability. See for example U.S. patentapplication Ser. No. 09/397,409, filed Sep. 16, 1999 and U.S. patentapplication Ser. No. 09/397,410, filed Sep. 16, 1999, which are bothherein fully incorporated by reference. However, as a result of usingthis combination, the improved supported catalyst composition becomessomewhat more difficult to feed to a reactor. The supported catalystbecomes sticky or statically inclined, thus preventing its continuousand smooth introduction into the reactor.

[0009] Thus, it would be advantageous to have an improved catalystcomposition that flows more easily and is capable of operating in apolymerization process continuously with enhanced reactor operability.

SUMMARY OF THE INVENTION

[0010] This invention provides a method of making a new and improvedflowing supported bulky ligand metallocene-type catalyst system thatcontains a carboxylate metal salt and for the catalyst systems use in apolymerizing process.

[0011] The invention also provides for a composition of a carboxylatemetal salt and a flow improver that is useful in a polymerizationprocess. In one embodiment, the flow improver is a colloidal particulatematerial.

[0012] In one embodiment, the method of the invention comprises the stepof combining, contacting, blending and/or mixing a catalyst system,preferably a supported catalyst system, with a carboxylate metal salt,and a flow improver. In one embodiment the catalyst system comprises aconventional-type transition metal catalyst compound. In the mostpreferred embodiment the catalyst system comprises a bulky ligandmetallocene-type catalyst compound. The combination of the catalystsystem, the carboxylate metal salt and the flow improver is useful inany olefin polymerization process. In the preferred method of theinvention, the carboxylate metal salt is contacted with the flowimprover prior to their use in the reactor or contact with apolymerization catalysts, preferably a supported polymerization catalytssystem. The preferred polymerization processes are a gas phase or aslurry phase process, most preferably a gas phase process. The mostpreferred flow improver is a colloidal particulate material such ascolloidal silica, for example snowtex.

[0013] In an embodiment, the invention provides for a method of making acatalyst composition useful for the polymerization of olefin(s), themethod including combining, contacting, blending and/or mixing apolymerization catalyst with at least one carboxylate metal salt and aflow improver. In an embodiment, the polymerization catalyst is aconventional-type transition metal polymerization catalyst, morepreferably a supported conventional-type transition metal polymerizationcatalyst. In the most preferred embodiment, the polymerization catalystis a bulky ligand metallocene-type catalyst, most preferably a supportedbulky ligand metallocene-type polymerization catalyst.

[0014] In one preferred embodiment, the invention is directed to acatalyst composition comprising a catalyst compound, preferably aconventional-type transition metal catalyst compound, more preferably abulky ligand metallocene-type catalyst compound, an activator and/orcocatalyst, a carrier, a carboxylate metal salt and a flow improver.

[0015] In the most preferred method of the invention, the carboxylatemetal salt and the flow improver is blended, preferably dry blended, andmost preferably tumble dry blended or fluidized, a supported catalystsystem or polymerization catalyst comprising a carrier. In this mostpreferred embodiment, the polymerization catalyst includes at least onebulky ligand metallocene-type catalyst compound, an activator and acarrier.

[0016] In yet another embodiment, the invention relates to a process forpolymerizing olefin(s) in the presence of a catalyst compositioncomprising a polymerization catalyst, a carboxylate metal salt and aflow improver, preferably the polymerization catalyst comprises acarrier, more preferably the polymerization catalyst comprises one ormore of combination of a conventional-type catalyst compound and/or abulky ligand metallocene-type catalyst compound.

[0017] In a preferred method for making the catalyst composition of theinvention, the method comprises the steps of combining a bulky ligandmetallocene-type catalyst compound, an activator and a carrier to form asupported bulky ligand metallocene-type catalyst system, contacting thesupported bulky ligand metallocene-type catalyst compound with acomposition of a carboxylate metal salt and a flow improver. In the mostpreferred embodiment, the supported bulky ligand metallocene-typecatalyst system, the carboxylate metal salt and the flow improvercomposition are in a substantially dry state or dried state.

[0018] In an embodiment, the invention provides for a process forpolymerizing olefin(s) in the presence of a polymerization catalysthaving been combined, contacted, blended, or mixed with a composition ofat least one carboxylate metal salt and at least one flow improver.

DETAILED DESCRIPTION OF THE INVENTION

[0019] Introduction

[0020] The invention is directed toward a method for making a supportedcatalyst system. It has been suprisingly discovered that by combining aflow improver with in particular a supported bulky ligandmetallocene-type catalyst system and a carboxylate metal salt, asupported catalyst system with improved flowability and operability isproduced. In addition it was also discovered that using the flowimprover with the supported catalyst system in a polymerization processresulted in an increase in the bulk density of resultant polymer. Theinvention also provides for the continuous flow of a supported catalystsystem to a polymerization process and a way to increase catalystproductivities to a commercially acceptable level with improved reactorprocess operability and polymer bulk density. Also, carboxylate metalsalts are difficult to handle, and in particular, because theirmorphology is poor, low bulk density, fluffy consistency, combining thecarboxylate metal salt with a supported catalyst system is a challenge.However, combining a carbxylate metal salt with a flow improversubstantially improves their handling as a composition of matter. Also,combining a carboxylate metal salt/flow improver composition with asupported catalyst system substantially is much improved.

[0021] Conventional-Type Transition Metal Catalysts

[0022] Conventional-type transition metal catalysts are thosetraditional Ziegler-Natta catalysts and Phillips-type chromium catalystwell known in the art. Examples of conventional-type transition metalcatalysts are discussed in U.S. Pat. Nos. 4,115,639, 4,077,904,4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741 all of whichare herein fully incorporated by reference. The conventional-typetransition metal catalyst compounds that may be used in the presentinvention include transition metal compounds from Groups III to VIII,preferably IVB to VIB of the Periodic Table of Elements.

[0023] These conventional-type transition metal catalysts may berepresented by the formula: MR_(x), where M is a metal from Groups IIIBto VIII, preferably Group IVB, more preferably titanium; R is a halogenor a hydrocarbyloxy group; and x is the valence of the metal M.Non-limiting examples of R include alkoxy, phenoxy, bromide, chlorideand fluoride. Non-limiting examples of conventional-type transitionmetal catalysts where M is titanium include TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl,Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl, Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃.1/3AlCl₃and Ti(OC₁₂H₂₅)Cl₃.

[0024] Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred. British PatentApplication 2,105,355, herein incorporated by reference, describesvarious conventional-type vanadium catalyst compounds. Non-limitingexamples of conventional-type vanadium catalyst compounds includevanadyl trihalide, alkoxy halides and alkoxides such as VOCl₃,VOCl₂(OBu) where Bu is butyl and VO(OC₂H₅)₃; vanadium tetra-halide andvanadium alkoxy halides such as VCl₄ and VCl₃(OBu); vanadium and vanadylacetyl acetonates and chloroacetyl acetonates such as V(AcAc)₃ andVOCl₂(AcAc) where (AcAc) is an acetyl acetonate. The preferredconventional-type vanadium catalyst compounds are VOCl₃, VCl₄ andVOCl₂—OR where R is a hydrocarbon radical, preferably a C₁ to C₁₀aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl,isopropyl, butyl, propyl, n-butyl, iso-butyl, tertiary-butyl, hexyl,cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates.

[0025] Conventional-type chromium catalyst compounds, often referred toas Phillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.2,285,721, 3,242,099 and 3,231,550, which are herein fully incorporatedby reference.

[0026] Still other conventional-type transition metal catalyst compoundsand catalyst systems suitable for use in the present invention aredisclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566 and5,763,723 and published EP-A2 0 416 815 A2 and EP-A1 0 420 436, whichare all herein incorporated by reference. The conventional-typetransition metal catalysts of the invention may also have the generalformula M′_(t)M″X_(2t)Y_(u)E, where M′ is Mg, Mn and/or Ca; t is anumber from 0.5 to 2; M″ is a transition metal Ti, V and/or Zr; X is ahalogen, preferably Cl, Br or I; Y may be the same or different and ishalogen, alone or in combination with oxygen, —NR₂, —OR, —SR, —COOR, or—OSOOR, where R is a hydrocarbyl radical, in particular an alkyl, aryl,cycloalkyl or arylalkyl radical, acetylacetonate anion in an amount thatsatisfies the valence state of M′; u is a number from 0.5 to 20; E is anelectron donor compound selected from the following classes ofcompounds: (a) esters of organic carboxylic acids; (b) alcohols; (c)ethers; (d) amines; (e) esters of carbonic acid; (f) nitriles; (g)phosphoramides, (h) esters of phosphoric and phosphorus acid, and (j)phosphorus oxy-chloride. Other catalysts may include cationic catalystssuch as AlCl₃, and other cobalt and iron catalysts well known in theart.

[0027] Typically, these conventional-type transition metal catalystcompounds excluding some convention-type chromium catalyst compounds areactivated with one or more of the conventional-type cocatalystsdescribed below.

[0028] Conventional-Type Cocatalysts

[0029] Conventional-type cocatalyst compounds for the aboveconventional-type transition metal catalyst compounds may be representedby the formula M³M⁴ _(v)X² _(c)R³ _(b-c), wherein M³ is a metal fromGroup IA, IIA, IIB and IIIA of the Periodic Table of Elements; M⁴ is ametal of Group IA of the Periodic Table of Elements; v is a number from0 to 1; each X² is any halogen; c is a number from 0 to 3; each R³ is amonovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4;and wherein b minus c is at least 1. Other conventional-typeorganometallic cocatalyst compounds for the above conventional-typetransition metal catalysts have the formula M³R³ _(k), where M³ is aGroup IA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium,barium, boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3depending upon the valency of M³ which valency in turn normally dependsupon the particular Group to which M³ belongs; and each R³ may be anymonovalent hydrocarbon radical.

[0030] Non-limiting examples of conventional-type organometalliccocatalyst compounds of Group IA, IIA and IIIA useful with theconventional-type catalyst compounds described above includemethyllithium, butyllithium, dihexylmercury, butylmagnesium,diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum,diisobutyl ethylboron, diethylcadmium, di-n-butylzinc andtri-n-amylboron, and, in particular, the aluminum alkyls, such astri-hexyl-aluminum, triethylaluminum, trimethylaluminum, andtri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude mono-organohalides and hydrides of Group IIA metals, and mono-or di-organohalides and hydrides of Group IIIA metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

[0031] For purposes of this patent specification and appended claimsconventional-type transition metal catalyst compounds exclude thosebulky ligand metallocene-type catalyst compounds discussed below.

[0032] Bulky Ligand Metallocene-Type Catalyst Compounds

[0033] Generally, bulky ligand metallocene-type catalyst compoundsinclude half and full sandwich compounds having one or more bulkyligands bonded to at least one metal atom. Typical bulky ligandmetallocene-type compounds are generally described as containing one ormore bulky ligand(s) and one or more leaving group(s) bonded to at leastone metal atom. In one preferred embodiment, at least one bulky ligandsis η-bonded to the metal atom, most preferably η⁵-bonded to the metalatom.

[0034] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

[0035] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention are represented by the formula:

L^(A)L^(B)MQ_(n)  (I)

[0036] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is a Group 4 transition metal,even more preferably M is zirconium, hafrium or titanium. The bulkyligands, L^(A) and L^(B), are open, acyclic or fused ring(s) or ringsystem(s) and are any ancillary ligand system, including unsubstitutedor substituted, cyclopentadienyl ligands or cyclopentadienyl-typeligands, heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (I) only one of either L^(A) or L^(B) is present.

[0037] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0038] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. For the purposes of this patent specification andappended claims the term “leaving group” is any ligand that can beabstracted from a bulky ligand metallocene-type catalyst compound toform a bulky ligand metallocene-type catalyst cation capable ofpolymerizing one or more olefin(s). In one embodiment, Q is amonoanionic labile ligand having a sigma-bond to M. Depending on theoxidation state of the metal, the value for n is 0, 1 or 2 such thatformula (I) above represents a neutral bulky ligand metallocene-typecatalyst compound.

[0039] Non-limiting examples of Q ligands include weak bases such asamines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicalshaving from 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

[0040] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention include those of formula (I) where L^(A) andL^(B) are bridged to each other by at least one bridging group, A, suchthat the formula is represented by

L^(A)AL^(B)MQ_(n)  (II)

[0041] These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (II) have two or morebridging groups A (EP 664 301 B1).

[0042] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those where the R substituents on the bulky ligands L^(A)and L^(B) of formulas (I) and (II) are substituted with the same ordifferent number of substituents on each of the bulky ligands. Inanother embodiment, the bulky ligands L^(A) and L^(B) of formulas (I)and (II) are different from each other.

[0043] Other bulky ligand metallocene-type catalyst compounds andcatalyst systems useful in the invention may include those described inU.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401,5,723,398, 5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158,5,900,517, 5,939,503 and 5,962,718 and PCT publications WO 93/08221, WO93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO98/46650, WO 99/02540 and WO 99/14221 and European publications EP-A-0578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839834, EP-B1-0 632 819, EP-B1-0 739 361, EP-B1-0 748 821 and EP-B1-0 757996, all of which are herein fully incorporated by reference.

[0044] In one embodiment, bulky ligand metallocene-type catalystscompounds useful in the invention include bridged heteroatom, mono-bulkyligand metallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all ofwhich are herein fully incorporated by reference.

[0045] In this embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(C)AJMQ_(n)  (III)

[0046] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillaryligand; and A is a bridging group; Q is a univalent anionic ligand; andn is the integer 0,1 or 2. In formula (III) above, L^(C), A and J form afused ring system. In an embodiment, L^(C) of formula (III) is asdefined above for L^(A), A, M and Q of formula (III) are as definedabove in formula (I).

[0047] In formula (III) J is a heteroatom containing ligand in which Jis an element with a coordination number of three from Group 15 or anelement with a coordination number of two from Group 16 of the PeriodicTable of Elements. Preferably J contains a nitrogen, phosphorus, oxygenor sulfur atom with nitrogen being most preferred.

[0048] In another embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057,all of which are herein fully incorporated by reference.

[0049] In an embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(D)MQ₂(YZ)X_(n)  (IV)

[0050] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; L^(D) is a bulky ligand that is bonded to M; each Q isindependently bonded to M and Q₂(YZ) forms a unicharged polydentateligand; A or Q is a univalent anionic ligand also bonded to M; X is aunivalent anionic group when n is 2 or X is a divalent anionic groupwhen n is 1; n is 1 or 2.

[0051] In formula (IV), L and M are as defined above for formula (I). Qis as defined above for formula (I), preferably Q is selected from thegroup consisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0052] In another embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095(dicarbamoyl metal complexes) and EP-A1-0 874 005 and U.S. Pat. No.5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and5,856,258 all of which are herein incorporated by reference.

[0053] In another embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

[0054] In one embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (V)

[0055] where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X,Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

[0056] Other Bulky Ligand Metallocene-Type Catalyst Compounds

[0057] It is within the scope of this invention, in one embodiment, thatthe bulky ligand metallocene-type catalyst compounds include complexesof Ni²⁺ and Pd²⁺ described in the articles Johnson, et al., “New Pd(II)-and Ni(II)-Based Catalysts for Polymerization of Ethylene anda-Olefins”, J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al.,“Copolymerization of Ethylene and Propylene with Functionalized VinylMonomers by Palladium(II) Catalysts”, J. Am. Chem. Soc., 1996, 118,267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S. Pat.Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fullyincorporated by reference. These complexes can be either dialkyl etheradducts, or alkylated reaction products of the described dihalidecomplexes that can be activated to a cationic state by the activators ofthis invention described below.

[0058] Also included as bulky ligand metallocene-type catalyst are thosediimine based ligands of Group 8 to 10 metal compounds disclosed in PCTpublications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem.Comm., pp. 849-850 (1998), all of which are herein incorporated byreference.

[0059] Other bulky ligand metallocene-type catalysts are those Group 5and 6 metal imido complexes described in EP-A2-0 816 384 and U.S. Pat.No. 5,851,945, which is incorporated herein by reference. In addition,bulky ligand metallocene-type catalysts include bridged bis(arylamido)Group 4 compounds described by D. H. McConville, et al., inOrganometallics 1195, 14, 5478-5480, which is herein incorporated byreference. In addition, bridged bis(amido) catalyst compounds aredescribed in WO 96/27439, which is herein incorporated by reference.Other bulky ligand metallocene-type catalysts are described asbis(hydroxy aromatic nitrogen ligands) in U.S. Pat. No. 5,852,146, whichis incorporated herein by reference. Other metallocene-type catalystscontaining one or more Group 15 atoms include those described in WO98/46651, which is herein incorporated herein by reference. Stillanother metallocene-type bulky ligand metallocene-type catalysts includethose multinuclear bulky ligand metallocene-type catalysts as describedin WO 99/20665, which is incorporated herein by reference.

[0060] It is also contemplated that in one embodiment, the bulky ligandmetallocene-type catalysts of the invention described above includetheir structural or optical or enantiomeric isomers (meso and racemicisomers, for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

[0061] Activator and Activation Methods for the Bulky LigandMetallocene-Type Catalyst Compounds

[0062] The above described bulky ligand metallocene-type catalystcompounds are typically activated in various ways to yield catalystcompounds having a vacant coordination site that will coordinate,insert, and polymerize olefin(s).

[0063] For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound or componentor method which can activate any of the bulky ligand metallocene-typecatalyst compounds of the invention as described above. Non-limitingactivators, for example may include a Lewis acid or a non-coordinatingionic activator or ionizing activator or any other compound includingLewis bases, aluminum alkyls, conventional-type cocatalysts andcombinations thereof that can convert a neutral bulky ligandmetallocene-type catalyst compound to a catalytically active bulkyligand metallocene cation. It is within the scope of this invention touse alumoxane or modified alumoxane as an activator, and/or to also useionizing activators, neutral or ionic, such as tri (n-butyl) ammoniumtetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983) or combinationthereof, that would ionize the neutral bulky ligand metallocene-typecatalyst compound.

[0064] In one embodiment, an activation method using ionizing ioniccompounds not containing an active proton but capable of producing botha bulky ligand metallocene-type catalyst cation and a non-coordinatinganion are also contemplated, and are described in EP-A-0 426 637, EP-A-0573 403 and U.S. Pat. No. 5,387,568, which are all herein incorporatedby reference.

[0065] There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166,5,856,256 and 5,939,346 and European publications EP-A-0 561 476,EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCT publicationWO 94/10180, all of which are herein fully incorporated by reference.

[0066] Organoaluminum compounds as activators include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

[0067] Ionizing compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

[0068] Other activators include those described in PCT publication WO98/07515 such as tris (2, 2′, 2″-nonafluorobiphenyl) fluoroaluminate,which publication is fully incorporated herein by reference.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference. WO 98/09996 incorporated herein by referencedescribes activating bulky ligand metallocene-type catalyst compoundswith perchlorates, periodates and iodates including their hydrates. WO98/30602 and WO 98/30603 incorporated by reference describe the use oflithium (2,2′-bisphenyl-ditrimethylsilicate).4THF as an activator for abulky ligand metallocene-type catalyst compound. WO 99/18135incorporated herein by reference describes the use oforgano-boron-aluminum activators. EP-B1-0 781 299 describes using asilylium salt in combination with a non-coordinating compatible anion.Also, methods of activation such as using radiation (see EP-B1-0 615 981herein incorporated by reference), electro-chemical oxidation, and thelike are also contemplated as activating methods for the purposes ofrendering the neutral bulky ligand metallocene-type catalyst compound orprecursor to a bulky ligand metallocene-type cation capable ofpolymerizing olefins. Other activators or methods for activating a bulkyligand metallocene-type catalyst compound are described in for example,U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO99/42467(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide),which are herein incorporated by reference.

[0069] It is also within the scope of this invention that the abovedescribed bulky ligand metallocene-type catalyst compounds can becombined with one or more of the catalyst compounds represented byformulas (I) through (V) with one or more activators or activationmethods described above.

[0070] It is further contemplated by the invention that other catalystscan be combined with the bulky ligand metallocene-type catalystcompounds of the invention. For example, see U.S. Pat. Nos. 4,937,299,4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of whichare herein fully incorporated herein reference. It is also contemplatedthat any one of the bulky ligand metallocene-type catalyst compounds ofthe invention have at least one fluoride or fluorine containing leavinggroup as described in U.S. application Ser. No. 09/191,916 filed Nov.13, 1998.

[0071] In another embodiment of the invention one or more bulky ligandmetallocene-type catalyst compounds or catalyst systems may be used incombination with one or more conventional-type catalyst compounds orcatalyst systems. Non-limiting examples of mixed catalysts and catalystsystems are described in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432,5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264,5,723,399 and 5,767,031 and PCT Publication WO 96/23010 published Aug.1, 1996, all of which are herein fully incorporated by reference.

[0072] Carboxylate Metal Salt

[0073] Carboxylate metal salts are well known in the art as additivesfor use with polyolefins, for example as a film processing aid. Thesetypes of post reactor processing additives are commonly used asemulsifying agents, antistat and antifogging agents, stabilizers,foaming aids, lubrication aids, mold release agents, nucleating agents,and slip and antiblock agents and the like. Thus, it was trulyunexpected that these post reactor agents or aids would be useful with apolymerization catalyst to improve the operability of a polymerizationprocess.

[0074] For the purposes of this patent specification and appended claimsthe term “carboxylate metal salt” is any mono- or di- or tri-carboxylicacid salt with a metal portion from the Periodic Table of Elements.Non-limiting examples include saturated, unsaturated, aliphatic,aromatic or saturated cyclic carboxylic acid salts where the carboxylateligand has preferably from 2 to 24 carbon atoms, such as acetate,propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate,t-butyl-acetate, caprylate, heptanate, pelargonate, undecanoate, oleate,octoate, palmitate, myristate, margarate, stearate, arachate andtercosanoate. Non-limiting examples of the metal portion includes ametal from the Periodic Table of Elements selected from the group of Al,Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na.

[0075] In one embodiment, the carboxylate metal salt is represented bythe following general formula:

M(Q)_(X)(OOCR)_(Y)

[0076] where M is a metal from Groups 1 to 16 and the Lanthanide andActinide series, preferably from Groups 1 to 7 and 13 to 16, morepreferably from Groups 3 to 7 and 13 to 16, even more preferably Groups2 and 13, and most preferably Group 13; Q is halogen, hydrogen, ahydroxy or hydroxide, alkyl, alkoxy, aryloxy, siloxy, silane sulfonategroup or siloxane; R is a hydrocarbyl radical having from 2 to 100carbon atoms, preferably 4 to 50 carbon atoms; and x is an integer from0 to 3 and y is an integer from 1 to 4 and the sum of x and y is equalto the valence of the metal. In a preferred embodiment of the aboveformula y is an integer from 1 to 3, preferably 1 to 2, especially whereM is a Group 13 metal.

[0077] Non-limiting examples of R in the above formula includehydrocarbyl radicals having 2 to 100 carbon atoms that include alkyl,aryl, aromatic, aliphatic, cyclic, saturated or unsaturated hydrocarbylradicals. In an embodiment of the invention, R is a hydrocarbyl radicalhaving greater than or equal to 8 carbon atoms, preferably greater thanor equal to 12 carbon atoms and more preferably greater than or equal to17 carbon atoms. In another embodiment R is a hydrocarbyl radical havingfrom 17 to 90 carbon atoms, preferably 17 to 72, and most preferablyfrom 17 to 54 carbon atoms.

[0078] Non-limiting examples of Q in the above formula include one ormore, same or different, hydrocarbon containing group such as alkyl,cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl,alkylsilane, arylsilane, alkylamine, arylamine, alkyl phosphide, alkoxyhaving from 1 to 30 carbon atoms. The hydrocarbon containing group maybe linear, branched, or even substituted. Also, Q in one embodiment isan inorganic group such as a halide, sulfate or phosphate.

[0079] In one embodiment, the more preferred carboxylate metal salts arethose aluminum carboxylates such as aluminum mono, di- andtri-stearates, aluminum octoates, oleates and cyclohexylbutyrates. Inyet a more preferred embodiment, the carboxylate metal salt is(CH₃(CH₂)₁₆COO)₃Al, a aluminum tri-stearate (preferred melting point115° C.), (CH₃(CH₂)₁₆COO)₂—Al—OH, a aluminum di-stearate (preferredmelting point 145° C.), and a CH₃(CH₂)₁₆COO—Al(OH)₂, an aluminummono-stearate (preferred melting point 155° C.).

[0080] Non-limiting commercially available carboxylate metal salts forexample include Witco Aluminum Stearate # 18, Witco Aluminum Stearate #22, Witco Aluminum Stearate # 132 and Witco Aluminum Stearate EA FoodGrade, all of which are available from Witco Corporation, Memphis, Tenn.

[0081] In one embodiment the carboxylate metal salt has a melting pointfrom about 30° C. to about 250° C., more preferably from about 37° C. toabout 220° C., even more preferably from about 50° C. to about 200° C.,and most preferably from about 100° C. to about 200° C. In a mostpreferred embodiment, the carboxylate metal salt is an aluminum stearatehaving a melting point in the range of from about 135° C. to about 165°C.

[0082] In another preferred embodiment the carboxylate metal salt has amelting point greater than the polymerization temperature in thereactor.

[0083] Other examples of carboxylate metal salts include titaniumstearates, tin stearates, calcium stearates, zinc stearates, boronstearate and strontium stearates.

[0084] The carboxylate metal salt in one embodiment may be combined withantistatic (agents such as fatty amines, for example, Kemamine AS 990/2zinc additive, a blend of ethoxylated stearyl amine and zinc stearate,or Kemamine AS 990/3, a blend of ethoxylated stearyl amine, zincstearate and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Boththese blends are available from Witco Corporation, Memphis, Tenn.

[0085] Flow Improvers

[0086] In the most preferred embodiment of the invention, the flowimprover is a colloidal silica, more specifically cabosil, which isavaiable from Cabot. In one embodiment, the flow improver is a fumedsilica. Non-limiting examples of flow improvers include cabosil,syloids, Snowtex products (available from Nissan Chemical Industries,Tokyo, Japan), alumina and the like. CAB-O-SIL M-5 is an untreatedamorphous fumed silica manufactured by Cabot. It is a high purity silicamanufactured by high temperature hydrolysis of chlorosilanes in ahydrogen/oxygen flame. Surface area 200 m²/g, bulk density 2.5 lb/ft³,average particule length 0.2-0.3 um.

[0087] Supports, Carriers and General Supporting Techniques

[0088] The above described bulky ligand metallocene-type catalystcompounds and catalyst systems may be combined with one or more supportmaterials or carriers using one of the support methods well known in theart or as described below. For example, in a most preferred embodiment,a bulky ligand metallocene-type catalyst compound or catalyst system isin a supported form, for example deposited on, contacted with, vaporizedwith, bonded to, or incorporated within, adsorbed or absorbed in, or on,a support or carrier.

[0089] The terms “support” or “carrier” are used interchangeably and areany support material, preferably a porous support material, includinginorganic or organic support materials. Non-limiting examples ofinorganic support materials include inorganic oxides and inorganicchlorides. Other carriers include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds, or anyother organic or inorganic support material and the like, or mixturesthereof.

[0090] The preferred carriers are inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, alumina, silica-alumina and mixtures thereof. Other usefulsupports include magnesia, titania, zirconia, magnesium chloride,montmorillonite (EP-B1 0 511 665), phyllosilicate, zeolites, talc, claysand the like. Also, combinations of these support materials may be used,for example, silica-chromium, silica-alumina, silica-titania and thelike. Additional support materials may include those porous acrylicpolymers described in EP 0 767 184 B1, which is incorporated herein byreference. Other support materials include nanocomposites as describedin PCT WO 99/47598, which is herein incorporated by reference.

[0091] It is preferred that the carrier, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 1000 m²/g, pore volume from about 0.8 to about 5.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the carrier of the invention typically has pore size in therange of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 450 Å.

[0092] Examples of supporting the bulky ligand metallocene-type catalystsystems of the invention are described in U.S. Pat. Nos. 4,701,432,4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892,5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766,5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015,5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402,5,731,261, 5,759,940, 5,767,032, 5,770,664, 5,846,895 and 5,939,348 andU.S. application Ser. Nos. 271,598 filed Jul. 7, 1994 and 788,736 filedJan. 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO 96/06187and WO 97/02297, and EP-B1-0 685 494 all of which are herein fullyincorporated by reference.

[0093] The method for making the catalyst composition generally involvesthe combining, contacting, blending, and/or mixing of a catalyst systemor polymerization catalyst with a composition of a carboxylate metalsalt and a flow improver.

[0094] In one embodiment of the method of the invention, aconventional-type transition metal catalyst and/or a bulky ligandmetallocene-type catalyst is combined, contacted, blended, and/or mixedwith a composition of at least one carboxylate metal salt and at leastone flow improver. In a most preferred embodiment, the conventional-typetransition metal catalyst and/or the bulky ligand metallocene-typecatalyst are supported on a carrier.

[0095] In another embodiment, the steps of the method of the inventioninclude forming a polymerization catalyst, preferably forming asupported polymerization catalyst, and contacting the polymerizationcatalyst with a composition of at least one carboxylate metal salt andat least one flow improver. In a preferred method, the polymerizationcatalyst comprises a catalyst compound, an activator or cocatalyst and acarrier, preferably the polymerization catalyst is a supported bulkyligand metallocene-type catalyst.

[0096] In one embodiment of the method of the invention the carboxylatemetal salt and flow improver composition is contacted with the catalystsystem, preferably a supported catalyst system, most preferably asupported bulky ligand metallocene-type catalyst system under ambienttemperatures and pressures. Preferably the contact temperature forcombining the polymerization catalyst and the carboxylate metalsalt/flow improver composition is in the range of from 0° C. to about100° C., more preferably from 15° C. to about 75° C., most preferably atabout ambient temperature and pressure.

[0097] In a preferred embodiment, the contacting of the polymerizationcatalyst, the carboxylate metal salt and the flow improver is performedunder an inert gaseous atmosphere, such as nitrogen. However, it iscontemplated that the combination of the polymerization catalyst, thecarboxylate metal salt and the flow improver may be performed in thepresence of olefin(s), solvents, hydrogen and the like.

[0098] In one embodiment, the carboxylate metal salt and/or flowimprover may be added at any stage during the preparation of thepolymerization catalyst.

[0099] In one embodiment of the method of the invention, thepolymerization catalyst and the carboxylate metal salt and/or the flowimprover composition are combined in the presence of a liquid, forexample the liquid may be a mineral oil, toluene, hexane, isobutane or amixture thereof. In a more preferred method the carboxylate metal saltand/or flow improver are combined with a polymerization catalyst thathas been formed in a liquid, preferably in a slurry, or combined with asubstantially dry or dried, polymerization catalyst that has been placedin a liquid and reslurried.

[0100] In an embodiment, the contact time for the carboxylate metal saltand/or the flow improver and the polymerization catalyst may varydepending on one or more of the conditions, temperature and pressure,the type of mixing apparatus, the quantities of the components to becombined, and even the mechanism for introducing the polymerizationcatalyst/carboxylate metal salt combination into the reactor.

[0101] Preferably, the polymerization catalyst, preferably a bulkyligand metallocene-type catalyst compound and a carrier, is contactedwith a carboxylate metal salt and the flow improver composition for aperiod of time from about a second to about 24 hours, preferably fromabout 1 minute to about 12 hours, more preferably from about 10 minutesto about 10 hours, and most preferably from about 30 minutes to about 8hours.

[0102] Preferably, the polymerization catalyst, preferably a bulkyligand metallocene-type catalyst compound, the activator and thecarrier, are contacted with the carboxylate metal salt and flow improvercomposition for a period of time from about a second to about 24 hours,preferably from about 1 minute to about 12 hours, more preferably fromabout 10 minutes to about 10 hours, and most preferably from about 30minutes to about 8 hours.

[0103] In an embodiment, the ratio of the weight of the carboxylatemetal salt to the weight of the transition metal of the catalystcompound is in the range of from about 0.01 to about 1000, preferably inthe range of from 1 to about 100, more preferably in the range of fromabout 2 to about 50, and most preferably in the range of from 4 to about20. In one embodiment, the ratio of the weight of the carboxylate metalsalt to the weight of the transition metal of the catalyst compound isin the range of from about 2 to about 20, more preferably in the rangeof from about 2 to about 12, and most preferably in the range of from 4to about 10.

[0104] In an embodiment, the weight percent of the flow improver to theweight of the total supported catalyst system (the catalyst compound,preferably a bulky ligand metallocene-type catalyst compound, theactivator, the carrier and the carboxylate metal salt) is in the rangeof from about 0.1 weight percent to about 50 weight percent, preferablyin the range of from 0.5 weight percent to about 25 weight percent, morepreferably in the range of from about 1 weight percent to about 10weight percent, and most preferably in the range of from 2 weightpercent to about 5 weight percent.

[0105] In another embodiment of the method of the invention, the weightpercent of the carboxylate metal salt based on the total weight of thepolymerization catalyst is in the range of from about 0.5 weight percentto about 500 weight percent, preferably in the range of from 1 weightpercent to about 25 weight percent, more preferably in the range of fromabout 2 weight percent to about 12 weight percent, and most preferablyin the range of from about 2 weight percent to about 10 weight percent.In another embodiment, the weight percent of the carboxylate metal saltbased on the total weight of the polymerization catalyst is in the rangeof from 1 to about 50 weight percent, preferably in the range of from 2weight percent to about 30 weight percent, and most preferably in therange of from about 2 weight percent to about 20 weight percent.

[0106] In one embodiment, where the process of the invention isproducing a polymer product having a density greater than 0.910 g/cc,the total weight percent of the carboxylate metal salt based on thetotal weight of the polymerization catalyst is greater than 1 weightpercent. In yet another embodiment, where the process of the inventionis producing a polymer product having a density less than 0.910 g/cc,the total weight percent of the carboxylate metal salt based on thetotal weight of the polymerization catalyst is greater than 3 weightpercent. If the polymerization catalyst includes a carrier, the totalweight of the polymerization catalyst includes the weight of thecarrier.

[0107] It is believed that the more metal of the activator, for exampletotal aluminum content or free aluminum content (the alkyl aluminumcontent in alumoxane), present in the polymerization catalyst, the morecarboxylate metal salt is required. Manipulating the amounts or loadingsof the polymerization catalyst components, i.e. the free aluminum mayprovide a means for adjusting the level of carboxylate metal salt.

[0108] Mixing techniques and equipment contemplated for use in themethod of the invention are well known. Mixing techniques may involveany mechanical mixing means, for example shaking, stirring, tumbling,and rolling. Another technique contemplated involves the use offluidization, for example in a fluid bed reactor vessel where circulatedgases provide the mixing. Non-limiting examples of mixing equipment forcombining, in the most preferred embodiment a solid polymerizationcatalyst and a solid carboxylate metal salt and flow improvercomposition, include a ribbon blender, a static mixer, a double coneblender, a drum tumbler, a drum roller, a dehydrator, a fluidized bed, ahelical mixer and a conical screw mixer.

[0109] In an embodiment of the method of the invention, a supportedconventional-type transition metal catalyst, preferably a supportedbulky ligand metallocene-type catalyst, is tumbled with a carboxylatemetal salt and/or a flow improver, preferably a composition of acarboxylate metal salt and a flow improver for a period of time suchthat a substantial portion of the supported catalyst is intimately mixedand/or substantially contacted with the carboxylate metal salt and/orflow improver.

[0110] In a preferred embodiment of the invention the catalyst system ofthe invention is supported on a carrier, preferably the supportedcatalyst system is substantially dried, preformed, substantially dryand/or free flowing. In an especially preferred method of the invention,the preformed supported catalyst system is contacted with a compositionof at least one carboxylate metal salt and at least one flow improver.The carboxylate metal salt and/or flow improver may be in solution orslurry or in a dry state, preferably the carboxylate metal salt and/orflow improver is in a substantially dry or dried state. In the mostpreferred embodiment, the carboxylate metal salt and flow improver iscontacted with a supported catalyst system, preferably a supported bulkyligand metallocene-type catalyst system in a rotary mixer under anitrogen atmosphere, most preferably the mixer is a tumble mixer, or ina fluidized bed mixing process, in which the polymerization catalyst,the carboxylate metal salt and the flow improver are in a solid state,that is they are both substantially in a dry state or in a dried state.

[0111] In some polymerization processes smaller particle size supportmaterials are preferred. However, the operability of these processes ismore challenging. It has been discovered that utilizing thepolymerization catalyst and carboxylate metal salt combination of theinvention, smaller particle size support materials may be usedsuccessfully. For example, silica having an average particle size fromabout 10 microns to 80 microns. Silica materials of this size areavailable from Crosfield Limited, Warrington, England, for exampleCrosfield ES-70 having an average particle size of 35 to 40 microns. Notwishing to bound by any theory, it is traditionally believed that usingsmaller average particle size supports produces more fines and resultsin a more sheeting prone supported catalyst. It is also believed thatthe use of a carboxylate metal salt with the polymerization catalystprovides for better particle growth during polymerization. This betterparticle morphology is believed to result in fewer fines and a reducedtendency for sheeting to occur. Thus, the use of a carboxylate metalsalt allows for the use of a smaller support material.

[0112] There are various other methods in the art for supporting apolymerization catalyst compound or catalyst system of the invention.For example, the bulky ligand metallocene-type catalyst compound of theinvention may contain a polymer bound ligand as described in U.S. Pat.Nos. 5,473,202 and 5,770,755, which is herein fully incorporated byreference; the bulky ligand metallocene-type catalyst system of theinvention may be spray dried as described in U.S. Pat. No. 5,648,310,which is herein fully incorporated by reference; the support used withthe bulky ligand metallocene-type catalyst system of the invention isfunctionalized as described in European publication EP-A-0 802 203,which is herein fully incorporated by reference, or at least onesubstituent or leaving group is selected as described in U.S. Pat. No.5,688,880, which is herein fully incorporated by reference.

[0113] In a preferred embodiment, the invention provides for a supportedbulky ligand metallocene-type catalyst system that includes a surfacemodifier that is used in the preparation of the supported catalystsystem as described in PCT publication WO 96/11960, which is hereinfully incorporated by reference. The catalyst systems of the inventioncan be prepared in the presence of an olefin, for example hexene-1.

[0114] A preferred method for producing a supported bulky ligandmetallocene-type catalyst system is described below and is described inU.S. application Ser. Nos. 265,533, filed Jun. 24, 1994 and 265,532,filed Jun. 24, 1994 and PCT publications WO 96/00245 and WO 96/00243both published Jan. 4, 1996, all of which are herein fully incorporatedby reference. In this preferred method, the bulky ligandmetallocene-type catalyst compound is slurried in a liquid to form ametallocene solution and a separate solution is formed containing anactivator and a liquid. The liquid may be any compatible solvent orother liquid capable of forming a solution or the like with the bulkyligand metallocene-type catalyst compounds and/or activator of theinvention. In the most preferred embodiment the liquid is a cyclicaliphatic or aromatic hydrocarbon, most preferably toluene. The bulkyligand metallocene-type catalyst compound and activator solutions aremixed together heated and added to a porous support, optionally a heatedporous support, or a porous support, optionally a heated porous supportis added to the solutions such that the total volume of the bulky ligandmetallocene-type catalyst compound solution and the activator solutionor the bulky ligand metallocene-type catalyst compound and activatorsolution is less than four times the pore volume of the porous support,more preferably less than three times, even more preferably less thantwo times; preferred ranges being from 1.1 times to 3.5 times range andmost preferably in the 1.2 to 3 times range.

[0115] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density of Fluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0116] The mole ratio of the metal of the activator component to themetal of the supported bulky ligand metallocene-type catalyst compoundsare in the range of between 0.3:1 to 1000:1, preferably 20:1 to 800:1,and most preferably 50:1 to 500:1. Where the activator is an ionizingactivator such as those based on the aniontetrakis(pentafluoro-phenyl)boron, the mole ratio of the metal of theactivator component to the metal component of the bulky ligandmetallocene-type catalyst is preferably in the range of between 0.3:1 to3:1.

[0117] In one embodiment of the invention, olefin(s), preferably C₂ toC₃₀ olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of the supportedbulky ligand metallocene-type catalyst system of the invention prior tothe main polymerization. The prepolymerization can be carried outbatchwise or continuously in gas, solution or slurry phase including atelevated pressures. The prepolymerization can take place with any olefinmonomer or combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference.

[0118] In an embodiment, the method of the invention provides forco-injecting an unsupported polymerization catalyst and a carboxylatemetal salt and a flow improver into the reactor. In one embodiment thepolymerization catalyst is used in an unsupported form, preferably in aliquid form such as described in U.S. Pat. Nos. 5,317,036 and 5,693,727and European publication EP-A-0 593 083, all of which are hereinincorporated by reference. The polymerization catalyst in liquid formcan be fed with a carboxylate metal salt and a flow improver, as a solidor a liquid, to a reactor using the injection methods described in PCTpublication WO 97/46599, which is fully incorporated herein byreference.

[0119] Where a carboxylate metal salt and an unsupported bulky ligandmetallocene-type catalyst system combination is utilized, the mole ratioof the metal of the activator component to the metal of the bulky ligandmetallocene-type catalyst compound is in the range of between 0.3:1 to10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to2000:1.

[0120] In one embodiment, the supported catalyst system containing acarboxylate metal salt and a flow improver, preferably the supportedbulky ligand metallocene-type catalyst system containing a carboxlatemetal salt and the flow improver have a average flow time less than 150seconds, preferably less than 100 seconds, more preferably less than 75seconds, even more preferably less than 50 seconds, still even morepreferably less than 40 seconds, and most preferably less than 20seconds.

[0121] Polymerization Process

[0122] The supported catalyst systems and/or compositions of theinvention described above are suitable for use in any prepolymerizationand/or polymerization process over a wide range of temperatures andpressures. The temperatures may be in the range of from −60° C. to about280° C., preferably from 50° C. to about 200° C., and the pressuresemployed may be in the range from 1 atmosphere to about 500 atmospheresor higher.

[0123] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene.

[0124] In one embodiment, the process of this invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the polymerizationof two or more olefin monomers of ethylene, propylene, butene-1,pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[0125] Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbomene, norbomadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbomene, dicyclopentadiene and cyclopentene.

[0126] In the most preferred embodiment of the process of the invention,a copolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

[0127] In another embodiment of the process of the invention, ethyleneor propylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

[0128] In one embodiment, the invention is directed to a polymerizationprocess, particlarly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene-type catalysts as described in U.S.Pat. Nos. 5,296,434 and 5,278,264, both of which are herein incorporatedby reference.

[0129] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0130] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0131] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110C, andmost preferably in the range of from about 70° C. to about 95° C.

[0132] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

[0133] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0134] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0135] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

[0136] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0137] Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525, whichare fully incorporated herein by reference

[0138] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the presence ofa bulky ligand metallocene-type catalyst system of the invention and inthe absence of or essentially free of any scavengers, such astriethylaluminum, trimethylaluminum, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. This preferred process is described in PCT publication WO 96/08520and U.S. Pat. No. 5,712,352 and 5,763,543, which are herein fullyincorporated by reference.

[0139] Polymer Products

[0140] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers.

[0141] The polymers, typically ethylene based polymers, have a densityin the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range offrom 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/ccto 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

[0142] The polymers produced by the process of the invention typicallyhave a molecular weight distribution, a weight average molecular weightto number average molecular weight (M_(w)/M_(n)) of greater than 1.5 toabout 15, particularly greater than 2 to about 10, more preferablygreater than about 2.2 to less than about 8, and most preferably from2.5 to 8.

[0143] Also, the polymers of the invention typically have a narrowcomposition distribution as measured by Composition Distribution BreadthIndex (CDBI). Further details of determining the CDBI of a copolymer areknown to those skilled in the art. See, for example, PCT PatentApplication WO 93/03093, published Feb. 18, 1993, which is fullyincorporated herein by reference.

[0144] The bulky ligand metallocene-type catalyzed polymers of theinvention in one embodiment have CDBI's generally in the range ofgreater than 50% to 100%, preferably 99%, preferably in the range of 55%to 85%, and more preferably 60% to 80%, even more preferably greaterthan 60%, still even more preferably greater than 65%.

[0145] In another embodiment, polymers produced using a bulky ligandmetallocene-type catalyst system of the invention have a CDBI less than50%, more preferably less than 40%, and most preferably less than 30%.

[0146] The polymers of the present invention in one embodiment have amelt index (MI) or (I₂) as measured by ASTM-D-1238-E in the range from0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/min toabout 100 dg/min, even more preferably from about 0.1 dg/min to about 50dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

[0147] The polymers of the invention in an embodiment have a melt indexratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to lessthan 25, more preferably from about 15 to less than 25.

[0148] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

[0149] In yet another embodiment, propylene based polymers are producedin the process of the invention. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117, all of which are herein incorporated byreference.

[0150] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes produced via conventional Ziegler-Nattaand/or bulky ligand metallocene-type catalysis, elastomers, plastomers,high pressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

[0151] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, pipe,geomembranes, and pond liners. Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollowarticles, rigid food containers and toys, etc.

[0152] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

COMPARATIVE EXAMPLE 1

[0153] Witco Aluminum Stearate #22 (AlSt #22) [CH₃(CH₂)₁₆COO]₂Al—OHavailable from Witco Corporation, Memphis, Tenn. was used. The untappedbulk density, and sieve flow characteristics of this sample weremeasured and recorded in Table 1.

COMPARATIVE EXAMPLE 2

[0154] Ten grams of Witco Aluminum Stearate #22 (AlSt #22)[CH₃(CH₂)₁₆COO]₂Al—OH available from Witco Corporation, Memphis, Tenn.as received from Witco was weighed into a 250 ml beaker. 50 ml ofisopropanol/deionized water mixture (50/50 by volume) was added to thebeaker. The slurry was stirred for 15 minutes at room temperature afterwhich the solvent was evaporated to dryness in an oil bath at 100° C.The white solid was further vacuum dried at 80° C. for 16 hours toinsure it was dry. The product was crushed with a spatula and sievedthrough a 40 mesh screen. The untapped bulk density and the sieve flowproperties of this material were measured and recorded in Table 1.

EXAMPLE 3

[0155] Ten grams of Witco Aluminum Stearate #22 (AlSt #22)[CH₃(CH₂)₁₆COO]₂Al—OH available from Witco Corporation, Memphis, Tenn.was weighed into a 250 ml beaker. The exact procedure used inComparative Example 2 was performed with the exception that in thisexample colloidal silica Snowtex PS-L available from Nissan ChemicalIndustries, Tokyo, Japan (2.35 ml containing 1 g silica in water) wasadded to the beaker and the procedure (drying, etc.) was continued as inComparative Example 2.

EXAMPLE 4

[0156] Ten grams of Witco Aluminum Stearate #22 (AlSt#22)[CH₃(CH₂)₁₆COO]₂Al—OH available from Witco Corporation, Memphis,Tenn. was weighed into a 250 ml beaker. The exact procedure used inComparative Example 2 was performed with the exception that in thisexample 2.35 ml of Snowtex PS-L slurry in water (1.0 silica equivalent)were added to 50 ml of MeOH which was then added to the 250 ml beaker.(Snowtex PS-L is available from Nissan Chemical Industries, Tokyo,Japan) After stirring, the solvents were removed by heating and thedried material treated similarly to the procedure used in ComparativeExample 2.

EXAMPLE 5

[0157] As above (Example 4) except that 7.0 ml of Snowtex PS-L slurry inwater (3.0 silica equivalent) were added instead of 2.35 ml. (SnowtexPS-L is available from Nissan Chemical Industries, Tokyo, Japan).

EXAMPLE 6

[0158] As above (Example 4) except that 2.28 ml of Snowtex MA/ST-Mslurry in water (1.0 g silica equivalent) were added instead of 2.35 mlof Snowtex PS-L. (Snowtex MA/ST-M L is available from Nissan ChemicalIndustries, Tokyo, Japan).

[0159] Procedure Used for Measuring Flow Properties

[0160] The following procedure outlines the steps followed to measurecatalyst flowability using the ATM Sonic Sifter. The test was used tocompare the various catalyst compositions by measuring the time it takesfor a 2.0 gram sample to pass through a selected sieve size. Thepreferred sieve size is 18 mesh or 1,000 microns. The sonic sifter wasused as a tapping device only with the amplitude for sifting mechanismset to zero. Because the catalyst samples tested are air and moisturesensitive, it is necessary to perform the test under anaerobicconditions.The steps were as follows:

[0161] 1) Two grams of the catalyst sample to be measured is weighedinto plastic boat with pour spout.

[0162] 2) The 18 mesh sieve is placed on the fines collection device anda plastic powder funnel with a 17 mm opening is placed on the top of thesieve.

[0163] 3) The 2.0 gram catalyst sample is poured down the slope of thefunnel.

[0164] 4) The funnel is slowly lifted and the catalyst sample is allowedto spread out on the top of the sieve.

[0165] 5) The five spacers are carefully placed above the 18 mesh screenand the stack is locked together.

[0166] 6) The assembly (screen and spacers) is placed inside of the testchamber of the sonic sifter.

[0167] 7) The arms holding the stack together are unlocked so that thesprings in the top of the assembly will operate freely.

[0168] 8) The amplitude setting is checked to make sure it is set tozero. The tapping function (one tap every 4 sec) only will be employed.

[0169] 9) The stopwatch is started when the first tap is observed.

[0170] 10) The stopwatch is stopped when the entire sample has passedthrough the sieve.

[0171] 11) The sonic sifter timer is then turned off.

[0172] 12) The stopwatch time is recorded in the lab notebook and theprocedure repeated.

[0173] The data for each of Comparative Examples 1 and 2 and Examples 3through 6 are represented in Table 1. TABLE 1 Bulky Density ImproverFlow Time Example (g/cc) (sec) CEx 1 0.25 102  CEx 2 0.27 124  3 0.35 564 0.37 44 5 0.37 50 6 0.35 44

[0174] The data in Table 1 illustrates that the bulk density increasedby 40 to 50 percent and the flow time is reduced by half indicatingsubstantially improved flow characteristics.

EXAMPLE 7

[0175] Preparation of a Supported Bulky Ligand Metallocene-Type CatalystSystem

[0176] Into a 2 gallon (7.57 liters) reactor was charged first with 2.0liters of toluene then, 1060 g of 30 wt % methylalumoxane solution intoluene (available from Albemarle, Baton Rouge, La.), followed by 23.1 gof bis(1,3-methyl-n-butyl cyclopentadienyl) zirconium dichloride as a10% solution in toluene. The mixture was stirred for 60 minutes at roomtemperature after which 850 g of silica (Davison 948 dehydrated at 600°C. available from W. R. Grace, Davison Chemical Division, Baltimore,Md.) was added to the liquid with slow agitation. Stirring speed wasincreased for approximately 10 minutes to insure dispersion of thesilica into the liquid and then appropriate amount of toluene was addedto make up a slurry of liquid to solid having a consistency of 4 cc/g ofsilica. Mixing was continued for 15 minutes at 120 rpm after which 6 gof Kemamine AS-990 (available Witco Corporation, Memphis, Tenn.) wasdissolved in 100 cc of toluene and was added and stirred for 15 minutes.Drying was then initiated by vacuum and some nitrogen purge at 175° F.(79.4° C.). When the polymerization catalyst comprising the carrier,silica, appeared to be free flowing, it was cooled down and dischargedinto a nitrogen purged vessel. An approximate yield of 1 Kg of drypolymerization catalyst was obtained due to some loses due to drying.

COMPARATIVE EXAMPLE 8

[0177] Blending with Supported Catalyst System

[0178] Prior to blending the composition, which in this ComparativeExample 8 only included the carboxylate metal salt (AlSt #22) asdescribed above in Comparative Example 1, with a supported catalystsystem prepared similarly to that in Example 7, the composition (onlythe carboxylate metal salt (AlSt #22)) sample was vacuum dried at 80° C.for 24 hours. Inside the dry box, 2000 milligram of the supportedcatalyst system and 60 milligram of the carboxylate metal salt (AlSt#22) and no flow improver was loaded into a 10 ml Hypo vial. With arubber septum put on, the vial was secured onto the end of metal rod.End to end rotation of vial was performed. The metal rod was turning ata speed of about 25 rpm. Total of 50 rotations were carried out on eachsample. The flow rate of the mixture was determined using the methoddescribed above, and the results of which appear in Table 2.

COMPARATIVE EXAMPLE 9

[0179] Blending with Supported Catalyst System

[0180] Prior to blending the composition, which in this ComparativeExample 9 only included the carboxylate metal salt (AlSt #22) and asolvent as described above in Comparative Example 2, with a supportedcatalyst system prepared similarly to that in Example 7, the composition(only the solvent treated carboxylate metal salt (AlSt #22)) sample wasvacuum dried at 80° C. for 24 hours. Inside the dry box, 2000 milligramof the supported catalyst system and 60 milligram of the carboxylatemetal salt (AlSt #22 of Comparative Example 2, which incorporated noflow improver was loaded into a 10 ml Hypo vial. With a rubber septumput on, the vial was secured onto the end of metal rod. End to endrotation of vial was performed. The metal rod was turning at a speed ofabout 25 rpm. Total of 50 rotations were carried out on each sample. Theflow rate of the mixture was determined using the method describedabove, and the results of which appear in Table 2.

EXAMPLE 10

[0181] Blending with Supported Catalyst System

[0182] In this Example 10, the composition described in Example 3 thatincluded a carboxylate metal salt and a flow improver as described abovein Example 3 was blended with a supported catalyst system preparedsimilarly to that in Example 7. The carboxylate metal salt (AlSt #22) ofExample 3, in this Example 10, was vacuum dried at 80° C. for 24 hours.Inside the dry box, 2000 milligram of the supported catalyst system anda composition of 60 milligram of the carboxylate metal salt (AlSt #22)and 10 weight percent (6 mg) of the flow improver prepared per Example 3(Snowtex PS-L) was loaded into a 10 ml Hypo vial. With a rubber septumput on, the vial was secured onto the end of metal rod. End to endrotation of vial was performed. The metal rod was turning at a speed ofabout 25 rpm. Total of 50 rotations were carried out on each sample. Theflow rate of the mixture was determined using the method describedabove, and the results of which appear in Table 2.

EXAMPLE 11

[0183] Blending with Supported Catalyst System

[0184] In this Example 11, the composition described in Example 4 thatincluded a carboxylate metal salt and a flow improver as described abovein Example 4 was blended with a supported catalyst system preparedsimilarly to that in Example 7. The carboxylate metal salt (AlSt #22) inthis Example 11 was vacuum dried at 80° C. for 24 hours. Inside the drybox, 2000 milligram of the supported catalyst system and a compositionof 60 milligram of the carboxylate metal salt (AlSt #22) and 10 weightpercent (6 mg) of the flow improver prepared per Example 4 (SnowtexPS-L) was loaded into a 10 ml Hypo vial. With a rubber septum put on,the vial was secured onto the end of metal rod. End to end rotation ofvial was performed. The metal rod was turning at a speed of about 25rpm. Total of 50 rotations were carried out on each sample. The flowrate of the mixture was determined using the method described above, andthe results of which appear in Table 2.

EXAMPLE 12

[0185] Blending with Supported Catalyst System

[0186] In this Example 12, the composition described in Example 5 thatincluded a carboxylate metal salt and a flow improver as described abovein Example 5 was blended with a supported catalyst system preparedsimilarly to that in Example 7. The carboxylate metal salt (AlSt #22) inthis Example 12 was vacuum dried at 80° C. for 24 hours. Inside the drybox, 2000 milligram of the supported catalyst system and a compositionof 60 milligram of the carboxylate metal salt (AlSt #22) and 30 weightpercent (18 mg) of the flow improver prepared per Example 5 (SnowtexPS-L) was loaded into a 10 ml Hypo vial. With a rubber septum put on,the vial was secured onto the end of metal rod. End to end rotation ofvial was performed. The metal rod was turning at a speed of about 25rpm. Total of 50 rotations were carried out on each sample. The flowrate of the mixture was determined using the method described above, andthe results of which appear in Table 2.

EXAMPLE 13

[0187] Blending with Supported Catalyst System

[0188] In this Example 13, the composition described in Example 6 thatincluded a carboxylate metal salt and a flow improver as described abovein Example 6 was blended with a supported catalyst system preparedsimilarly to that in Example 7. The carboxylate metal salt (AlSt #22) inthis Example 13 was vacuum dried at 80° C. for 24 hours. Inside the drybox, 2000 milligram of the supported catalyst system and a compositionof 60 milligram of the carboxylate metal salt (AlSt #22) and 10 weightpercent (6 mg) of the flow improver used in Example 6 Snowtex MA/ST-Mwas loaded into a 10 ml Hypo vial. With a rubber septum put on, the vialwas secured onto the end of metal rod. End to end rotation of vial wasperformed. The metal rod was turning at a speed of about 25 rpm. Totalof 50 rotations were carried out on each sample. The flow rate of themixture was determined using the method described above, and the resultsof which appear in Table 2. TABLE 2 Flow Average Improver Flow TimeExample (wt. %) (seconds) CEx 8  0 86 CEx 9 solvent 86 10 10 66 11 10 4212 30 50 13 10 48

[0189] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that twoor more supported catalyst compositions of the invention can be used.For this reason, then, reference should be made solely to the appendedclaims for purposes of determining the true scope of the presentinvention.

We claim:
 1. A catalyst composition comprising, in combination, apolymerization catalyst comprising a bulky ligand metallocene-typecatalyst compound, a carboxylate metal salt and a flow improver.
 2. Thecatalyst composition of claim 1 wherein the carboxylate metal salt isrepresented by the formula: MQ_(x)(OOCR)_(y) where M is a metal from thePeriodic Table of Elements; Q is halogen, or a hydroxy, alkyl, alkoxy,aryloxy, siloxy, silane or sulfonate group; R is a hydrocarbyl radicalhaving from 2 to 100 carbon atoms; x is an integer from 0 to 3; y is aninteger from 1 to 4; and the sum of x and y is equal to the valence ofthe metal M; Q is halogen or a hydroxy group, and R is a hydrocarbylradical having from 4 to 24 carbon atoms.
 3. The catalyst composition ofclaim 2 wherein y is either 1 or 2, M is a Group 2 or 13 metal, Q is ahydroxy group, and R is a hydrocarbyl radical having greater than 12carbon atoms.
 4. The catalyst composition of claim 1 wherein thecarboxylate metal salt is a stearate compound.
 5. The catalystcomposition of claim 1 wherein the flow improver is a colloidal silica.6. A method for making a catalyst composition, the method comprising thesteps of: (a) forming a polymerization catalyst comprising a bulkyligand metallocene-type catalyst compound; (b) adding a carboxylatemetal salt; and (c) adding at least one flow improver.
 7. The method ofclaim 6 wherein the polymerization catalyst is dry and free flowing andthe flow improver is a solid form.
 8. The method of claim 6 wherein thecarboxylate metal salt is represented by the formula: MQ_(x)(OOCR)_(y)where M is a metal from the Periodic Table of Elements; Q is halogen, ora hydroxy, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group; Ris a hydrocarbyl radical having from 2 to 100 carbon atoms; x is aninteger from 0 to 3; y is an integer from 1 to 4; and the sum of x and yis equal to the valence of the metal M; Q is halogen or a hydroxy group,and R is a hydrocarbyl radical having from 4 to 24 carbon atoms.
 9. Themethod of claim 6 wherein the carboxylate metal salt and the flowimprover are combined prior to adding to the polymerization catalyst.10. The method of claim 6 wherein the flow improver is a colloidalsilica.
 11. A continuous process for polymerizing olefin monomer(s) in areactor under polymerization conditions, the process comprising thesteps of: introducing olefin monomer(s) to the reactor; (i) introducinga polymerization catalyst comprising a bulky ligand metallocene-typecatalyst compound; (ii) a carboxylate metal salt; and (iii) a flowimprover; and withdrawing a polymer product from the reactor.